Graphene supercapacitor design and manufacture

ABSTRACT

Improvements in design and manufacturing techniques to produce a graphene based prismatic supercapacitor of very high capacitance with very high energy density storage able to outperform and replace the cutting edge batteries available in the market today.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional PatentApplication No. 62/340,119 filed May 23, 2016 entitled GRAPHENESUPERCAPACITOR DESIGN AND MANUFACTURE which is hereby incorporatedherein by reference in the entirety.

FEDERALLY SPONSORED RESEARCH

Not Applicable

SEQUENCE LISTING OR PROGRAM

Not Applicable

FIELD OF THE INVENTION

The present invention is related to improvements in design andmanufacturing techniques to produce a graphene based prismaticsupercapacitor of very high capacitance with very high energy densitystorage able to outperform and replace the cutting edge batteriesavailable in the market today.

Background

Graphene and other nano technology carbon based materials have attracteda lot of attention recently in a lot of areas. Specifically, in batteryand capacitor technology, they provide a means to produce cheapconductors of very high conductance that dramatically increase surfacearea available for electrostatic charge accumulation in asupercapacitor.

Many research lines are seeking ways to further improve surface area,energy density and power density with promising results. Once fullydeveloped into a mature technology, graphene supercapacitors offer thepromise of affordable, clean and recyclable devices able to vastlyoutperform the best batteries available in the market today. To achievethat goal though, there are still many aspects of the design andmanufacturing of supercapacitors that need improvement.

Prior Art

There have been many approaches to the construction of carbon basedsupercapacitors. The basic concept is very straightforward. Two carbonbased electrodes are put in contact with a suitable electrolyte thataccumulates charge via an electrostatic process. The advantage of usingcarbon is that this is a cheap, readily available material that isextremely versatile and can be made into electrodes with very highsurface area relatively easily. Furthermore, carbon remains stable whensubjected to a wide range of electrolytes allowing for a wider range ofoptions in design.

Activated carbon, graphene, carbon nanotubes and other carbon basedmaterials have been tried and results have been presented by severalindividuals and research institutions. So far most reports seem toindicate that for a given electrolyte, reducing the size of theelectrodes so that a higher number of electrodes can fit into a givenvolume increases the energy density of the device and increasing thesurface area for a given electrode size increases the power density.

As a result, activated carbon has been proposed as a convenient materialsince it has a very high surface area with respect to its volume and isvery cheap to obtain and use. Activated carbon has the disadvantagethough of being harder to morph into small consistent electrodes thatwill remain stable during the lifetime of the device. Graphene offersthe advantage of potentially higher surface area with respect to volumeand the possibility of producing very small electrodes. However,graphene is more expensive to produce and more complicated to manipulatethan activated carbon.

There are many companies already manufacturing carbon basedsupercapacitors that offer good performance for specific applications.However, until now the commercial devices have been unable to deliversufficient energy and power densities at an affordable price to beconsidered for replacement of the cutting edge lithium ion batteriesavailable in the market.

The main reason for the unsatisfactory performance is the constructiondesign used by most existing supercapacitors that are constructed usinga stack of pairs of solid plates made of carbon (graphene, activatedcarbon, etc.), each plate producing an electrode. Each pair of plateelectrodes is separated by an insulator to prevent short circuits shouldthe plates touch. This design relies solely on the high surface area anindividual plate has due to the nature of the carbon electrode that is afunction of the plate area. Limitations regarding the structuralstrength of the plates require them to have a minimum thickness and theneed of an insulator sheet between each pair of plate electrodes furtherlimits the total surface area that is made available for a given volume(mass) resulting in poor energy density.

The technology is advancing at a rapid pace and it is reasonable toassume that in the near future supercapacitors will improve to the pointthat they will displace batteries in a very wide range of applications.Improved manufacturing techniques using activated carbon, graphene orother materials such as carbon nanotubes or mixtures of more than onetype of material may in the future provide a better compromise forenergy density, power density and cost.

Advantages

The proposed invention has been designed considering multiple aspects ofthe production of a graphene or activated carbon supercapacitor andoffers the following advantages:

1) Massive increase in available surface area of the electrodes bymorphing them into lines with very small width and relatively highheight separated by very small gaps instead of a simple solid plateresulting in high specific capacitance;

2) Increase in energy density by allowing the reliable construction ofthe electrodes using thin substrates;

3) Increase in power density by using large terminals and avoidingdamage to the microstructure of the electrodes sometimes caused by stepsof other unperfected manufacturing processes;

4) Simplification of the manufacturing process, allowing the electrodesand electrolyte to be printed even at very small sizes;

5) Simplification of the packaging, allowing the several printed sheetsthat constitute a particular device to be simply stacked and encased ina simple process that does not require high precision positioning nordelicate tasks;

6) Significant cost reduction in the production of the devices; and

7) Enable the use of special inks made of graphene, activated carbon,carbon nanotubes or a mixture of two or more of these components orother materials that may be determined in the future to be advantageousto use.

SUMMARY OF THE INVENTION

One object and advantage of the proposed invention is the printing ofthe supercapacitor individual elements in suitable sheets so that thesesheets can be easily stacked saving time and money in the assemblyprocess.

Another object and advantage of the proposed invention is innovativenanolinear patterns and shapes that may be printed or formed using othermanufacturing processes to produce individual elements of thesupercapacitor that provide improvements in attainable capacitance,improvements in attainable energy density, improvements in attainablepower density, improvements in electrical insulation or maximum breakdown voltage, improvements in charge and discharge performance,improvements in mechanical resistance to shock and improvements in thedevice useful life.

Another object and advantage of the proposed invention is themanufacturing process that allows existing printing equipment normallyused to produce printed plastic films for packaging or similarapplications to print the nanolinear patterns and shapes necessary toproduce a supercapacitor. The existing printing equipment maximumresolution is typically 5 microns or more, meaning that features smallerthan that cannot be reliably printed. The manufacturing method of thepresent invention, combined with the proposed nanolinear patterns andshapes allows the existing printing equipment to be tuned so that it canprint reliably and cheaply features smaller than 5 microns, reaching 1micron or less.

Another object and advantage of the proposed invention is amanufacturing process using photoresist that allows affordable andreliable printing of even smaller electrodes than the printing processcan produce. The photoresist process can achieve a consistent resolutionof 50 nanometers producing electrodes that are sufficiently precise anduniform to achieve high energy densities at the same time avoiding shortcircuits or performance degradation of the assembled device due tonon-uniformities among the several individual sheets used in itsconstruction.

Another object and advantage of the proposed invention is thepossibility to use special inks composed of graphene, graphene oxide,activated carbon, carbon nanotubes or a mixture of two or more of thesecomponents or other components that may be determined in the future tobe advantageous to use.

Another object and advantage of the present invention is the containmentprocess used in the printing process that uses high viscosity inks thatare cured with ultraviolet light or heat to print the small features ofthe nanolinear patterns and shapes of the present invention along thedirection of printing. As all small printed lines within the nanolinearpatterns are parallel to the direction of printing, the viscous ink willpreferable flow in the direction of printing and eventual spills combineinto the same line being printed. Ultraviolet light or heat can be usedto quickly dry the ink that has just been deposited into the substrateavoiding spills perpendicular to the direction of printing that wouldcause parallel lines to touch producing short circuits.

Another object and advantage of the present invention is the containmentprocess used in a photoresist process that is suitable for printing atnanometer scales where high viscosity inks do not produce a good result.The ink is applied during the printing process into gaps left by removedareas of the photoresist. The ink cannot fill the spaces still coveredby the photoresist that work as barriers to the coating of the ink onthe substrate or element sheet. As a result, the ink can be made withtiny particles using a hinder of low viscosity or may be made with abinder that will not harden unless submitted to a suitable curingprocess. This allows the ink to reach all spots intended to be coveredwithout the risk of leaks or spills that could lead to short circuits.The ink can be submitted to a curing process or left to dry on its ownbefore the physical barrier of the photoresist is removed so that theelectrolyte can be applied or deposited only in the areas previouslyoccupied by the photoresist.

Another object and advantage of the proposed invention is themanufacturing process that allows the affordable and reliable assemblyof sheets printed using the printing or photoresist process into stacksand then into devices with the desired electric characteristics.

Another object and advantage of the present invention is the creation ofelectrical contact points along the edges of each substrate or elementsheet to enable conductivity simply by stacking the sheets.

Another object and advantage of the present invention is an increase inthe number of capacitors within a given area through the formationphysical barriers that contain and provide for increases in thethickness of the graphene ink thereby increasing the surface area of theelectrodes.

The present invention is related to a manufacturing process for theproduction of supercapacitors having increased energy density,comprising perforating a series of orifices on an element sheet;layering the element sheet with photoresist on one or both sides;exposing portions of the photoresist to a light source to remove theseportions from the element sheet; printing graphene ink within theremaining portions of the photoresist and through the orifices; printinggraphene ink on both sides of the element sheet filling the orifices tocreate terminals that have a larger size as compared to the remainingportions and to connect both sides of the element sheet; removingremaining portions of photoresist thereby leaving a pattern design;printing electrolyte within the pattern design; and wherein the patterndesign forming electrodes having minimal spacing between gaps toincrease the energy density within the supercapacitor. The manufacturingprocess for the production of supercapacitors wherein the minimal gapsbetween the printed electrodes is less than five microns. Themanufacturing process for the production of supercapacitors wherein theminimal gaps between the printed electrodes is between one hundred nanometers to two microns. The manufacturing process for the production ofsupercapacitors comprising increasing the thickness of the photoresistto increase the depth of the graphene ink layer and the electrolytelayer thereby increasing the energy density of the supercapacitor. Themanufacturing process for the production of supercapacitors comprisingreplacing the graphene ink by an ink composed of a mixture selected fromthe group consisting of graphene, carbon nanotubes and activated carbonto increase the physical properties of the electrodes by increasing thenumber of pores into the electrodes thereby increasing the availablesurface area of the printed electrode and thereby increasing thecapacitance and the energy density of the supercapacitor. Themanufacturing process for the production of supercapacitors comprising apattern design having physical barriers that extend linearly in thedirection of printing. The supercapacitor produced by the process ofmanufacturing. The manufacturing process for the production ofsupercapacitors comprising a pattern design that maximizes the number ofindividual capacitors that can be printed within the element sheet. Themanufacturing process for the production of supercapacitors comprisingindividual capacitors connected in parallel. The manufacturing processfor the production of supercapacitors comprising individual capacitorsconnected in series. The manufacturing process for the production ofsupercapacitors comprising individual capacitors connected in series andparallel. The manufacturing process for the production ofsupercapacitors comprising a pattern design comprising individualfringes of the electrode terminating in a curved end with a matchingcurved contour on an adjacent electrode. The manufacturing process forthe production of supercapacitors comprising stacking element sheets inparallel to increase the capacitance and the current of thesupercapacitor. The manufacturing process for the production ofsupercapacitors comprising stacking element sheets in series to increasethe voltage of the supercapacitor. The manufacturing process for theproduction of supercapacitors comprising stacking element sheets inseries and parallel to increase the voltage, capacitance and current ofthe supercapacitor.

The present invention is further related to an increased energy densitysupercapacitor, comprising a pattern design developed using aphotoresist process; graphene ink printed within the pattern design;electrolyte printed within and covering the pattern design; and whereinthe individual capacitors dimensions are reduced to fit more capacitorswithin a given area to form an increased energy density supercapacitor.The increased energy density supercapacitor wherein the minimaldimension of a line of graphene ink printed is less than 5 microns. Theincreased energy density supercapacitor wherein the minimal dimension ofa line of graphene ink printed is between one hundred nano meters andtwo microns. The increased energy density supercapacitor wherein thesupercapacitor may be stacked in parallel to increase capacitance andcurrent. The increased energy density supercapacitor wherein thesupercapacitor may be stacked in series to increase voltage. Theincreased energy density supercapacitor of claim wherein thesupercapacitor may be stacked in series and parallel to increasevoltage, capacitance and current. The increased energy densitysupercapacitor wherein the graphene ink is replaced by an ink composedof a mixture selected from the group consisting of graphene, carbonnanotubes and activated carbon to increase the physical properties ofthe electrodes by increasing the number of pores into the electrodesthereby increasing the available surface area of the printed electrodeand thereby increasing the capacitance and the energy density of thesupercapacitor.

The present invention is further related to a manufacturing process forthe production of thin line supercapacitors having increased energydensity, comprising perforating a series of orifices on an elementsheet; printing graphene ink on both sides of the element sheet fillingthe orifices to create terminals that connect both sides of the elementsheet; printing graphene ink in a plurality of thin lines perpendicularto the terminals and along the direction of printing; printingelectrolyte within the plurality of thin lines; and forming electrodeshaving minimal spacing between gaps to increase the energy densitywithin the supercapacitors. The manufacturing process for the productionof thin line supercapacitors wherein the minimal gaps between printedfeatures is less than ten microns. The manufacturing process for theproduction of thin line supercapacitors wherein the minimal gaps betweenprinted features is between two hundred nano meters and ten microns. Themanufacturing process for the production of thin line supercapacitorscomprising printing short thin lines that are in parallel to theplurality of thin lines and that do not connect to the terminals therebycreating additional capacitors in series to increase voltage. Themanufacturing process for the production of thin line supercapacitorscomprising replacing the graphene ink by an ink composed of a mixtureselected from the group consisting of graphene, carbon nanotubes andactivated carbon to increase the physical properties of the electrodesby increasing the number of pores into the electrodes thereby increasingthe available surface area of the printed electrode and therebyincreasing the capacitance and the energy density of the supercapacitor.The supercapacitor produced by the manufacturing process. Themanufacturing process for the production of thin line supercapacitorscomprising a pattern design formed from the plurality of thin lines thatmaximizes the number of individual capacitors that can be printed withinthe element sheet. The manufacturing process for the production of thinline supercapacitors comprising individual capacitors connected inparallel. The manufacturing process for the production of thin linesupercapacitors comprising individual capacitors connected in series.The manufacturing process for the production of thin linesupercapacitors comprising the individual capacitors connected in seriesand parallel. The manufacturing process for the production of thin linesupercapacitors comprising stacking element sheets in parallel toincrease the capacitance and the current of the supercapacitor. Themanufacturing process for the production of thin line supercapacitorscomprising stacking element sheets in series to increase the voltage ofthe supercapacitor. The manufacturing process for the production of thinline supercapacitors comprising stacking element sheets in series andparallel to increase the voltage, capacitance and current of thesupercapacitor.

These and other features, advantages and improvements according to thisinvention will be better understood by reference to the followingdetailed description and accompanying drawings.

DRAWINGS—FIGURES

Various other objects, features and attendant advantages of the presentinvention will become fully appreciated as the same becomes betterunderstood when considered in conjunction with the accompanyingdrawings, in which like reference characters designate the same orsimilar parts throughout the several views, and wherein:

FIG. Description Drawing #  1 Element sheet with perforations forparallel construc- 1 tion top view  1A Element sheet with perforationsfor parallel construc- 1 tion side view  2 Element sheet withperforations for series construc- 1 tion top view  2A Element sheet withperforations for series construc- 1 tion side view  3 Perforationformation method of the element sheet 2  4 Photoresist applied toparallel sheet 3  5 Image projected into photoresist 4  6 Manufacturingmethod to project image into 5 photoresist  7 Image imprinted into toplayer photoresist 6  7A Detail view of photoresist top layer withimprinted 6 image  8 Photoresist top layer developed areas removed 7  8ADetail view of photoresist top layer with developed 7 areas removed  9Photoresist bottom layer with developed areas removed 8 10 Ink appliedinto photoresist top layer removed areas 9 10A Detail view of inkapplied into photoresist top layer 9 removed areas 11 Ink overflowcausing short circuits 10 12 Polishing process to remove ink overflow 1113 Resulting printed features into element sheet after 12 allphotoresist removed 13A Detail of printed features 12 14 Electrolyte andglue applied to element sheet 13 15 Printed nanolinear pattern for afull parallel element 14 top view 15A Printed nanolinear pattern for afull parallel element 14 for parallel staking side view 15B Printednanolinear pattern for a full parallel element 14 for series stackingside view 16 Printed nanolinear pattern for a 2 series element 15 17Printed nanolinear pattern for a 3 series element 16 18 Printednanolinear pattern for a 4 series element 17 19 Printed nanolinearpattern for a half full series 18 element 20 Printed nanolimear patternfor a full series element 19 21 Thick terminals printed overperforations in direction 20 transversal to printing 22 Thin linesprinted parallel to direction of printing 21 for a full parallel element23 Thin lines printed parallel to direction of printing 22 for a 2series element 24 Thin lines printed parallel to direction of printing23 for a 3 series element 25 Manufacturing process 24 26 Stack ofsupercapacitor elements arranged in parallel 25 27 Stack ofsupercapacitor elements arranged in series 25 28 Stack of supercapacitorelements arranged in 2 series 26 of 3 paralleled elements 29 Stack ofsupercapacitor elements arranged in 3 series 26 of 2 paralleled elements30 Isometric exploded view of supercapacitor unit 27 31 Isometric viewof parallel supercapacitor with 27 prismatic case drawn in phantom lines31A Detail view of power lid connection to terminal of 27 parallelsupercapacitor 32 Isometric view of series supercapacitor with 28prismatic case drawn in phantom lines 32A Detail view of power lidconnection to terminal of 28 series supercapacitor 33 Isometric view ofalternate construction of 28 supercapacitor 33A Detail view of power lidconnection to terminal of 28 alternate supercapacitor 33B Detail view ofpower lid clearance of alternate 28 supercapacitor 34 Isometric view ofanother alternate construction of 28 supercapacitor 35 Cross-sectionalview of a portion of the element sheet 29 36 Cross-sectional view of aportion of the photomask 29 37 Standard deposition of ink into amaterial sheet 29 38 Cross-sectional view of the filling of thephotoresist 29 gaps with ink 39 Process step of removing the remainingphotoresist 29 40 Process step of printing electrolyte 29

DRAWINGS - REFERENCE NUMERALS N Item Name Shown in FIGS. 42 elementsheet 1 1A 2 2A 3 4 5 6 7 7A 8 8A 9 10 10A 11 12 13 14 15 15A 15B 16 1718 19 20 21 22 23 24 26 27 28 29 35 36 37 38 39 40 43 orifices 1 1A 2 2A3 4 8A 9 15 15A 15B 21 35 36 38 39 40 44 perforation drum 3 25 45perforation spikes 3 46 photoresist 4 5 6 7A 8A 9 10A 11 35 36 47pattern mask 5 36 48 lens 5 49 light source 5 36 39 50 cylindricalpattern mask 6 51 mask gap 6 52 linear light source 6 53 illuminatedareas 7A 54 removed areas 8A 9 55 cavities 8A 9 10A 36 56 physicalbarriers 8A 9 10A 36 38 57 printer head 10 37 38 40 58 ink 10A 11 12 3839 40 59 ink remover 12 60 terminal 13 14 15 15A 15B 16 17 18 19 20 2122 23 24 26 27 30 31A 32A 33A 33B 61 electrode A 13 15 16 17 18 19 20 62electrode B 13 15 16 17 18 19 20 63 electrolyte 14 15 15A 15B 26 27 4064 glue strip 14 15 15A 15B 65 fringe 15 16 17 18 19 20 66 electrode gap15 16 17 18 19 20 67 electrode connection 15 16 17 18 19 20 68 electrodeconnection gap 15 16 17 18 19 20 69 curved end 15 16 17 18 19 20 22 2324 70 curved contour 15 16 17 18 19 20 71 series electrode 16 17 18 1920 72 printed layer 15 15A 15B 26 27 73 parallel design 15 74 series 2design 16 75 series 3 design 17 76 series 4 design 18 77 series halffull design 19 78 series full design 20 79 thin line 22 23 24 80 thinline extra run 22 23 24 81 short thin line 23 24 82 sheet heel 25 83continuous sheet 25 84 work station 25 85 guide roller 25 86 stackedsheet 25 87 width cut sheet 25 88 length cut sheet 25 89 parallel stack26 30 31 90 series stack 27 32 91 2 series 3 parallel stack 28 33 92 3series 2 parallel stack 29 93 terminal connection 26 27 28 29 94 seriesgap 27 28 29 95 cover element 26 27 28 29 96 electrolyte seal 30 97terminal seal 30 98 case 30 31 32 33 99 device terminal 30 31 31A 32 32A33 33A 33B 34 100 device connection 31A 32A 33A 101 device terminalbypass 33B

DETAILED DESCRIPTION

The present invention consists of pattern designs and methods to produceaffordable high quality supercapacitors that have high energy densityand high power density. The groundbreaking pattern designs of thepresent invention optimize useable surface area within a substrate bycreating linear barriers at distances that are only nanometers apart.The nanolinear pattern designs formed from the linear and other physicalbarriers once transferred to a suitable substrate are the basic elementsto build the supercapacitor. The nanolinear patterns can be made usinggraphene ink, graphene oxide ink, other inks based on other carboncomponents such as activated carbon or carbon nanotubes, or using an inkbased on a mixture of these components. The linear barriers extend inthe direction of applying ink to the substrate and provide for ink tothicken along the linear barriers increasing the height of the ink inrelation to the substrate and thereby increasing the surface area of theelectrode which provides for increases in energy density and powerdensity of the supercapacitor.

FIG. 1 shows a top view of an element sheet 42 a used to manufacture oneelement of the supercapacitor that is tailored to be used in parallel.In this case, the element sheet 42 a is perforated by a series oforifices 43 a, 43 b on both extremities.

FIG. 1A shows a front view of an element sheet 42 b used to manufactureone element of the supercapacitor that is tailored to be used inparallel. In this case, the element sheet 42 b is perforated by a seriesof orifices 43 c, 43 d on both extremities.

FIG. 2 shows a top view of the element sheet 42 a used to manufactureone element of the supercapacitor that will be used in series. In thiscase, the element sheet 42 a is perforated by a series of orifices 43 aon only one extremity.

FIG. 2A shows a front view of the element sheet 42 b used to manufactureone element of the supercapacitor that will be used in series. In thiscase, the element sheet 42 b is perforated by a series of orifices 43 con only one extremity.

The element sheet 42 is made of a printable isolating material such asacetate or plastic film as thin as practical to avoid surface defectsand structural weakness.

FIG. 3 shows an isometric view of a perforation drum 44 that can be usedto produce the orifices 43 a and 43 b into the element sheet 42. Theperforation drum 44 has a series of perforation spikes 45 a and 45 bthat may be heated for better results. As the perforation drum 44rotates in the direction of the curved arrow, the element sheet 42advances in synchronicity in the direction of the straight arrow, theperforation spikes 45 a and 45 b produce the orifices 43 a and 43 b inthe intended positions in the element sheet.

FIG. 4 shows an isometric view of the element sheet 42 coated with alayer of a photoresist 46 that is used to allow the printing or otherprocess of application of the conductors on a very small scale therebyproviding improvements in the performance of the supercapacitor. Theorifices 43 a, 43 b are visible in dashed lines.

FIG. 5 shows an isometric view of an apparatus that may be used tosensitize the photoresist 46 a and 46 b that has been applied ordeposited on both sides of the element sheet 42. A light source 49produces a light of adequate wavelength that goes through a lens 48 oran adequate apparatus to illuminate a pattern mask 47 having the linearand physical barriers to form the unique nanolinear pattern designs.Thenanolinear pattern design image is produced on the surface of theelement sheet 42 to sensitize the photoresist. The process is repeatedfor both sides of the element sheet.

FIG. 6 shows an isometric view of another apparatus that is moreadequate for mass production that may be used to sensitize thephotoresist 46 a and 46 b that has been deposited into both sides of theelement sheet 42. A linear light source 52 produces a focused andcollimated light of adequate wavelength that illuminates a cylindricalpattern mask 50 producing a dynamic image of the nanolinear patterndesign into the surface of the element sheet 42. As the cylindricalpattern mask 50 rotates in the direction of the curved arrow, theelement sheet 42 advances in synchronicity in the direction of thestraight arrow, sensitizing the photoresist as it moves beneath thecylindrical pattern mask 50. A mask gap 51 generates a gap between twoconsecutive element sheets so they can later on be cut apart. Theprocess is repeated for both sides of the element sheet.

FIG. 7 shows an isometric view of the element sheet 42 coated with thephotoresist that has been sensitized to create a desired nanolinearpattern design of the present invention that will be created in thesheet.

Detail FIG. 7A shows a series of illuminated areas 53 of the sensitizedphotoresist 46 to produce the desired pattern (in hatched lines) thatwill be created in the element sheet 42.

FIG. 8 shows an isometric view of the element sheet 42 coated with thephotoresist that has been sensitized and developed removing the materialto create a negative image of the intended nanolinear pattern.

Detail FIG. 8A shows the photoresist 46 applied on the top of theelement sheet 42 with a series of removed areas 54 that create a seriesof cavities 55 that are surrounded by physical barriers 56 creating anegative image of the intended nanolinear pattern. The parallel linearbarriers formed with curves and other shapes may be only nanometersapart to define the electrical connections of the electrodes. Theremoval of material of the photoresist 46 exposes the orifices 43 sothat when the graphene ink (or other suitable ink) is applied to theorifices the ink is allowed to flow through to connect both sides of theelement sheet 42.

FIG. 9 shows the photoresist 46 applied on the bottom of the elementsheet 42 with a series of removed areas 54 that create a negative imageof the intended printing pattern. The removal of material of thephotoresist 46 creates cavities 55 that expose the orifices 43 that aresurrounded by physical barriers 56 so that when the graphene ink (orother suitable ink) is applied to the orifices the ink is allowed toflow through to connect both sides of the element sheet 42 providing anelectrical connection along the extremities of each side of elementsheet 42.

FIG. 10 shows an isometric view of the element sheet 42 as the removedareas of the photoresist are being filled with ink supplied by a printerhead 57.

Detail FIG. 10A shows that as adequate ink 58 is deposited, theremaining photoresist 46 acts as physical barriers 56 that contain theink 58 forcing it to exactly match the intended nanolinear pattern to beleft into the element sheet 42.

FIG. 11 shows an isometric view of the element sheet 42 as thedeposition of ink has finished. The photoresist 46 has confined the inkinto the photoresist free areas 58 a, 58 b, and 58 c producing theintended nanolinear pattern. However, some ink may still overflow orspill over the top of the photoresist 46 barrier producing undesireddeposits of ink 58 d, 58 e, 58 f, etc. that need to be removed to avoidshort circuits.

FIG. 12 shows an isometric view of the element sheet 42 as thedeposition of ink has finished. The photoresist 46 has confined the inkinto the photoresist free areas 58 a, 58 b producing the intendednanolinear pattern. An ink remover 59 such as through polishing is thenused to eliminate the undesired deposits of ink producing a perfectsheet with no short circuits.

FIG. 13 shows an isometric view of the element sheet 42 drawn in phantomlines to show the resulting printed features.

Detail FIG. 13A shows that the process produces a terminal that is madeof two halves 60 a and 60 b connected by a series of bridges 60 c madeof ink that had passed through the orifices made into the element sheet.The electrode A 61 and the electrode B 62 can also be seen (see FIG.15).

FIG. 14 shows an isometric view of the element sheet 42 as a glue strip64 and an electrolyte 63 are applied. The electrolyte 63 is applied ontop of the nanolinear pattern design covering everything exceptterminals 60 a and 60 b. The glue strip 64 encircles the electrolyte 63and both terminals 60 a and 60 b providing a containment to theelectrolyte 63 and helps to secure the terminals in place once theelement sheets are stacked (see FIG. 26, FIG. 27, FIG. 28, and FIG. 29).

FIG. 15 shows a top view of the element sheet 42 a printed with thenanolinear pattern in a parallel design 73. The parallel design 73 isused to maximize the number of individual capacitors that can be printedinto a sheet using the most effective nanolinear pattern, that haslinear barriers that extend in the direction of printing to minimizeprinting complexity and by doing so reduce costs and printing errors.The parallel design 73 is composed of a pair of terminals 60 a and 60 bthat will become the positive and negative poles of the capacitor. Theterminal 60 a is connected to an electrode A 61 and the terminal 60 b isconnected to an electrode B 62 by a series of electrode connections 67leaving a series of electrode connection gaps 68 that expose thematerial of the element sheet 42.

The electrode A 61 and the electrode B 62 have a series of intertwinedfringes 65 that are separated by an electrode gap 66 that meandersbetween them. To facilitate the identification of the individual fringesthe electrode A 61 is drawn with 45 degree left to right hatched linesand the electrode B 62 is drawn with 45 degree right to left hatchedlines.

To avoid spiked edges that have a concentrating effect on the electricalfield that would negatively impair the performance of the supercapacitordevice, each of the individual fringes of the electrodes terminate in acurved end 69 that is matched by a curved contour 70 on the otherelectrode. A layer of a suitable electrolyte 63 a is printed on the topof the parallel design 73 covering all fringes of both the electrode A61 and the electrode B 62 but leaving the electrode connection gaps 68uncovered. In that way when a group of element sheets are stacked toproduce a supercapacitor device, the electrolyte 63 a can be sealedinside the stack by melting a thin strip of material of the elementsheets or applying a glue strip 64 a along the line passing at themiddle of the electrode connection gaps 68 on both extremities of theelement sheets and around the outermost fringes of the electrode A 61and the electrode B 62 (see FIG. 33).

FIG. 15A shows a front view of the element sheet 42 b that has theprinted layer 72 b with two terminals 60 c and 60 d that both extend tothe other side of the printed layer 72 b in case of an element sheettailored to be used in parallel. The orifices 43 a, 43 b drawn in dashedlines connect the terminals in one side of the element sheet to thecorresponding terminals on the other side. The electrolyte 63 b isapplied on top of the printed layer 72 b. The glue strip 64 b encirclesthe element sheet 42 b.

FIG. 15B shows a front view of the element sheet 42 c that has theprinted layer 72 c with only one terminal 60 e that extends to the otherside of the printed layer 72 c in case of an element sheet tailored tobe used in series. The orifices 43 c drawn in dashed lines connect theterminal in one side of the element sheet to the corresponding terminalon the other side. The electrolyte 63 c is applied on top of the printedlayer 72 c. The glue strip 64 c encircles the element sheet 42 c.

Each set of one fringe of the electrode A and one fringe of theelectrode B implement one individual capacitor. The fringes are made asthin as possible and as high as possible to maximize the surface areathat each individual element sheet can contain. The height of thefringes can be controlled by varying the thickness of the appliedphotoresist.

FIG. 16 shows a top view of the element sheet 42 printed with ananolinear pattern series 2 design 74. The series 2 design 74 iscomposed of a pair of terminals 60 a and 60 b that will become thepositive and negative poles of the capacitor. The terminal 60 a isconnected to several electrode A 61 a, 61 b, etc. and the terminal 60 bis connected to several electrode B 62 a, 62 b, etc. by a series ofelectrode connections 67 leaving a series of electrode connection gaps68 that expose the material of the element sheet 42. Between the fringes65 of each pair of electrodes, a series electrode 71 a, 71 b, etc. isintroduced creating two capacitors in series arranged in severalparallel blocks. All electrode fringes are separated by electrode gaps66. To facilitate the identification of the individual fringes theelectrode A 61 is drawn with 45 degree left to right hatched lines andthe electrode B 62 is drawn with 45 degree right to left hatched lineswhile the series electrode 71 is left unmarked.

To avoid spiked edges that have a concentrating effect on the electricalfield that would negatively impair the performance of the supercapacitordevice, the individual fringes 65 of the electrodes terminate in curvedends 69 matched by curved contours 70 on the other electrode wheneverapplicable.

Each set of one fringe of the electrode A, one fringe of the electrode Band the fringe of the series electrode between them implement twoindividual capacitors connected in series. The fringes are made as thinas possible and as high as possible to maximize the surface area thateach individual element sheet can contain. The height of the fringes canbe controlled by varying the thickness of the applied photoresist.

FIG. 17 shows a top view of the element sheet 42 printed with ananolinear pattern series 3 design 75. The series 3 design 75 iscomposed of the terminals 60 a and 60 b that will become the positiveand negative poles of the capacitor. The terminal 60 a is connected toseveral electrode A 61 a, 61 b, etc. and the terminal 60 b is connectedto several electrode B 62 a, 62 b, etc. by electrode connections 67leaving electrode connection gaps 68 that expose the material of theelement sheet 42. Between the fringes 65 of each pair of electrodes, twoseries electrodes 71 a, 71 b, 71 c, 71 d, etc. are introduced creatingthree capacitors in series arranged in several parallel blocks. Allelectrode fringes are separated by electrode gaps 66. To facilitate theidentification of the individual fringes the electrode A 61 is drawnwith 45 degree left to right hatched lines and the electrode B 62 isdrawn with 45 degree right to left hatched lines while the serieselectrode 71 is left unmarked.

To avoid spiked edges that have a concentrating effect on the electricalfield that would negatively impair the performance of the supercapacitordevice, the individual fringes of the electrodes terminate in curvedends 69 matched by curved contours 70 on the other electrode wheneverapplicable.

Each set of one fringe of the electrode A, one fringe of the electrode Band the two fringes of the series electrode between them implement threeindividual capacitors connected in series. The fringes are made as thinas possible and as high as possible to maximize the surface area thateach individual element sheet can contain. The height of the fringes canbe controlled by varying the thickness of the applied photoresist.

FIG. 18 shows a top view of the element sheet 42 printed with ananolinear pattern series 4 design 76. The series 4 design 76 iscomposed of the terminals 60 a and 60 b that will become the positiveand negative poles of the capacitor. The terminal 60 a is connected toseveral electrode A 61 a, 61 b, etc. and the terminal 60 b is connectedto several electrode B 62 a, 62 b, etc. by electrode connections 67leaving electrode connection gaps 68 that expose the material of theelement sheet 42. Between the fringes 65 of each pair of electrodes,three series electrodes 71 a, 71 b, 71 c, etc. are introduced creatingfour capacitors in series. All electrode fringes are separated byelectrode gaps 66. To facilitate the identification of the individualfringes the electrode A 61 is drawn with 45 degree left to right hatchedlines and the electrode B 62 is drawn with 45 degree right to lefthatched lines while the series electrode 71 is left unmarked.

To avoid spiked edges that have a concentrating effect on the electricalfield that would negatively impair the performance of the supercapacitordevice, the individual fringes of the electrodes terminate in curvedends 69 matched by curved contours 70 on the other electrode wheneverapplicable.

Each set of one fringe of the electrode A, one fringe of the electrode Band the three fringes of the series electrode between them implementfour individual capacitors connected in series. The fringes are made asthin as possible and as high as possible to maximize the surface areathat each individual element sheet can contain. The height of thefringes can be controlled by varying the thickness of the appliedphotoresist.

FIG. 19 shows a top view of the element sheet 42 printed with ananolinear pattern series half full design 77. The series half fulldesign 77 is composed of the terminals 60 a and 60 b that will becomethe positive and negative poles of the capacitor. The terminal 60 a isconnected to two electrode A 61 a and 61 b, and the terminal 60 b isconnected to one electrode B 62 by electrode connections 67 leavingelectrode connection gaps 68 that expose the material of the elementsheet 42. Between the fringes 65 of each pair of electrodes, severalseries electrodes 71 a, 71 b, etc. are introduced creating severalcapacitors in series arranged in two parallel blocks. All electrodefringes are separated by electrode gaps 66. To facilitate theidentification of the individual fringes the electrode A 61 is drawnwith 45 degree left to right hatched lines and the electrode B 62 isdrawn with 45 degree right to left hatched lines while the serieselectrodes 71 are left unmarked.

To avoid spiked edges that have a concentrating effect on the electricalfield that would negatively impair the performance of the supercapacitordevice, the individual fringes of the electrodes terminate in curvedends 69 matched by, curved contours 70 on the other electrode wheneverapplicable.

FIG. 20 shows a top view of the element sheet 42 printed with ananolinear pattern series full design 78. The series full design 78 iscomposed of the terminals 60 a and 60 b that will become the positiveand negative poles of the capacitor. The terminal 60 a is connected toone electrode A 61 and the terminal 60 b is connected to one electrode B62 by electrode connections 67 leaving electrode connection gaps 68 thatexpose the material of the element sheet 42. Between the fringes 65 ofthe electrodes, several series electrodes 71 a, 71 b, 71 c, etc. areintroduced creating several capacitors in series arranged in one block.All electrode fringes are separated by electrode gaps 66. To facilitatethe identification of the individual fringes the electrode A 61 is drawnwith 45 degree left to right hatched lines and the electrode B 62 isdrawn with 45 degree right to left hatched lines while the serieselectrodes 71 are left unmarked.

To avoid spiked edges that have a concentrating effect on the electricalfield that would negatively impair the performance of the supercapacitordevice, the individual fringes of the electrodes terminate in curvedends 69 matched by curved contours 70 on the other electrode wheneverapplicable.

Other configurations that produce other arrangements of m paralleledsets of n capacitors in series can be easily produced by altering thepattern of electrode A, electrode B and series electrodes that may beprinted or otherwise applied to the element sheet 42.

In another embodiment of the invention, FIG. 21 shows a top view of anelement sheet 42 on which two terminals 60 a and 60 b are printeddirectly on top of orifices 43 a, 43 b using traditional printingtechniques that do not require photoresist. The terminals 60 a and 60 bare printed as a thick Line perpendicular to the direction of theprinting (indicated by the straight arrow) and are made with a sizeslightly bigger than necessary to accommodate small subsequent printingerrors.

FIG. 22 shows a top view of an element sheet 42 with two terminals 60 aand 60 b printed as explained in FIG. 21. A pattern consisting of aseries of thin lines 79 a, 79 b, etc printed in the direction ofprinting (indicated by the straight arrow) is then added to the elementsheet 42 in such a way that alternating thin lines start at one terminaland do not reach the other. The thin lines 79 a, 79 b, etc. mayterminate in curved ends 69 or not depending on the level of controlthat the printer equipment can offer. To ensure proper operation eachthin line 79 a, 79 b, etc. have a thin line extra run 80 a, 80 b, etc.that advances over the recently printed terminal to which the line issupposed to be connected and terminates at a safe distance from theother. As the terminals are made larger than necessary, the thin linepattern is printed in the direction of the printing and the thin linesare printed overrunning the terminals, small errors in the positioningof the thin line pattern can be accommodated. As a result this designenables existing printing equipment to be tuned to produce thin lines asthin as 1 micron, separated by gaps of 1 micron when their normalmaximum resolution would be 5 microns or more.

The thin lines implement the electrodes of individual capacitors and aremade as thin as possible and as high as possible to maximize the surfacearea that each individual element sheet can contain. The height of thethin lines can be controlled by varying the viscosity of the ink: usinga more viscous ink produces a higher line. Depending on the process,quick drying ink or ink that cures with UV light or using another methodmay be applied to further increase the attainable height of the thinlines.

The pattern illustrated in FIG. 22 produces an element sheet with allindividual capacitors arranged in parallel. This configuration issimilar to the one described in FIG. 15.

FIG. 23 shows a top view of an element sheet 42 with two terminals 60 aand 60 b printed as explained in FIG. 21. A pattern consisting of aseries of thin lines 79 a, 79 b, etc and short thin lines 81 a, 81 b,etc. printed in the direction of printing (indicated by the straightarrow) is then added to the element sheet 42 in such a way thatalternating thin lines 79 a, 79 b, etc start at one terminal and do notreach the other and the short thin lines 81 a, 81 b, etc. do not toucheither one of the terminals. The thin lines 79 a, 79 b, etc. and theshort thin lines 81 a, 81 b, etc. may terminate in curved ends 69 or notdepending on the level of control that the printer equipment can offer.To ensure proper operation the thin lines 79 a, 79 b, etc. have thinline extra runs 80 a, 80 b, etc. that advance over the recently printedterminal to which the line is supposed to be connected and terminates ata safe distance from the other. As the terminals are made larger thannecessary, the thin line and short thin line pattern is printed in thedirection of the printing and the thin lines are printed overrunning theterminals, small errors in the positioning of the thin line and shortthin line pattern can be accommodated. As a result this design enablesexisting printing equipment to be tuned to produce thin lines and shortthin lines as thin as 1 micron, separated by gaps of 1 micron when theirnormal maximum resolution would be 5 microns or more.

The pattern illustrated in FIG. 23 with one short thin line printedbetween every two thin lines produces an element sheet with inparalleled sets of 2 capacitors in series, where m depends on the widthof the element sheet and the thickness of the thin lines and short thinlines printed. This configuration is similar to the one described inFIG. 16.

The thin lines and the short thin lines implement the electrodes ofindividual capacitors and are made as thin as possible and as high aspossible to maximize the surface area that each individual element sheetcan contain. The height of the thin lines and the short thin lines canbe controlled by varying the viscosity of the ink: using a more viscousink produces a higher line. Depending on the process, quick drying inkor ink that cures with UV light or using another method may be appliedto further increase the attainable height of the thin lines and theshort thin lines.

FIG. 24 shows a top view of an element sheet 42 with two terminals 60 aand 60 b printed as explained in FIG. 21. A pattern consisting of aseries of thin lines 79 a, 79 b, etc and short thin lines 81 a, 81 b,etc. printed in the direction of printing (indicated by the straightarrow) is then added to the element sheet 42 in such a way thatalternating thin lines 79 a, 79 b, etc start at one terminal and do notreach the other and the short thin lines 81 a, 81 b, etc. do not toucheither one of the terminals. The thin lines 79 a, 79 b, etc. and theshort thin lines 81 a, 81 b, etc. may terminate in curved ends 69 or notdepending on the level of control that the printer equipment can offer.To ensure proper operation the thin lines 79 a, 79 b, etc. have thinline extra runs 80 a, 80 b, etc. that advance over the recently printedterminal to which the line is supposed to be connected and terminates ata safe distance from the other. As the terminals are made larger thannecessary, the thin line and short thin line pattern is printed in thedirection of the printing and the thin lines are printed overrunning theterminals, small errors in the positioning of the thin line and shortthin line pattern can be accommodated. As a result this design enablesexisting printing equipment to be tuned to produce thin lines and shortthin lines as thin as 1 micron, separated by gaps of 1 micron when theirnormal maximum resolution would be 5 microns or more.

The pattern illustrated in FIG. 24 with two short thin lines printedbetween every two thin lines produces an element sheet with m paralleledsets of 3 capacitors in series, where m depends on the width of theelement sheet and the thickness of the thin lines and short thin linesprinted. This configuration is similar to the one described in FIG. 17.

Other configurations, similar to the ones described in in FIG. 18, FIG.19, and FIG. 20 as well as other arrangements of m paralleled sets of ncapacitors in series can be easily produced by altering the pattern ofthin lines and short thin lines printed.

FIG. 25 shows an isometric view of a manufacturing method that canproduce large quantities of element sheets stacked on top of each otherat an affordable cost. A sheet heel 82 of thin plastic film, containingup to several kilometers of a continuous sheet 83 a is unrolled to feedthe machinery. The continuous sheet 83 a is first perforated using theperforation drum 44 or other suitable method to produce orifices in therequired locations. The continuous sheet 83 a then passes through aseries of work stations 84 a, 84 b, 84 c, etc. where the other steps ofthe process are carried out.

In the printing process, work station 84 a prints the terminals, workstation 84 b prints the selected pattern of thin lines and short thinlines, work station 84 c dispenses the electrolyte and the glue strip.

In the photoresist process, work station 84 a dispenses the photoresist,work station 84 b sensitizes the photoresist using a cylindrical patternmask as described in FIG. 6 or another suitable method. The work station84 c removes the areas of the photoresist and subsequent work stations(not drawn to avoid cluttering) dispense the ink, remove eventual inkspills, remove the remaining photoresist, dispense the electrolyte andthe glue strip.

Several continuous sheets 83 b, 83 c, 83 d, 83 e, etc. under tension toallow the proper alignment of the terminals using guide rollers 85 a, 85b, etc. are then pressed together and glued producing a stacked sheet86. The stacked sheet 86 is cut first in the direction of the movementproducing parallel width cut sheets 87 that are subsequently cut in theperpendicular direction of the movement producing length cut sheets 88in the designed size. Depending on the sequence of the element sheetsprinted into the different continuous sheets, a variety of stacks can beproduced.

FIG. 26 shows a front view of a parallel stack 89 that is composed ofseveral element sheets 42 a, 42 b, 42 c, etc. with identical nanolinearpattern designs or printed thin line and short thins line patterns andidentical terminal configurations that have been made with terminals 60a, 60 b, etc. on both sides of both extremities. The element sheets 42a, 42 b, 42 c, etc. with their corresponding printed layers 72 a, 72 b,etc. and their layers of electrolyte 63 a, 63 b, 63 c, etc. are stackedon top of each other and each terminal on the top of an element sheetgets in contact with the corresponding terminal on the bottom of thenext element sheet producing a set of terminal connections 93. Theelectrolyte applied to an element sheet is contained by the elementsheet where the electrolyte has been applied and the next element sheet.A cover element 95 consisting of a element sheet with all terminals butno electrodes and no electrolyte is placed on the top to contain theelectrolyte of the previous element sheet closing the parallel stack 89.

FIG. 27 shows a front view of a series stack 90 that is composed ofseveral element sheets 42 a, 42 b, 42 c, etc. with identical nanolinearpattern designs or printed thin line and short thins line patterns andidentical terminal configurations that have been made with terminals 60a, 60 b, etc. on both extremities on the top but only one extremity onthe bottom 60 c. The element sheets 42 a, 42 b, 42 c, etc. with theircorresponding printed layers 72 a, 72 b, etc. and their layers ofelectrolyte 63 a, 63 b, etc. are stacked on top of each otheralternating the orientation so that the terminals 60 c on the bottom arelocated on the left side in one layer and on the right side on the nextlayer of the stack. One terminal on every element sheet does not have acorresponding terminal on the bottom of the next element sheet andbecause the element sheet is made of a material that is not a conductorof electricity, a series gap 94 is produced. The terminal on the top ofthe next element sheet on the same side of the stack has a matchingterminal on the bottom of the next element sheet producing a terminalconnection 93. This arrangement alternates from left to right at eachsubsequent layer producing series connections of all element sheets onthe series stack 90. The electrolyte applied to an element sheet iscontained by the element sheet where the electrolyte has been appliedand the next element sheet. The cover element 95 with terminals on thesame side and on only one extremity on the top and on the bottom, andwith no electrodes and no electrolyte is placed on the top of the stackto contain the electrolyte of the previous element sheet closing theseries stack 90.

FIG. 28 shows front view of a 2 series 3 parallel stack 91 that iscomposed of element sheets with identical nanolinear pattern designs orprinted thin line and short thins line patterns and different terminalconfigurations. The element sheets 42 a, and 42 d have been made withterminals on both extremities on the top but only one extremity on thebottom and are stacked at alternating orientations. The element sheets42 b, 42 c, 42 e, 42 f have been made with terminals on both extremitieson the top and on the bottom. The electrolyte applied to an elementsheet is contained by the element sheet where the electrolyte has beenapplied and the next element sheet. The cover element 95 with terminalson the same side and on only one extremity on the top and on the bottom,and with no electrodes and no electrolyte is placed on the top of thestack to contain the electrolyte of the previous element sheet closingthe 2 series 3 parallel stack 91.

The series gap 94 a in the middle divides the 2 series 3 parallel stack91 in two blocks, each made with three element sheets. The first blockis made by element sheets 42 a, 42 b, and 42 c connected by the terminalconnections 93 a, 93 b, 93 c, and 93 d. The second block is made byelement sheets 42 d, 42 e, and 42 f connected by the terminalconnections 93 f, 93 g, 93 h, and 93 i. The two blocks are connected inseries by the terminal connection 93 e. The terminal connections 93 jmakes the connection to the cover element 95 and the series gap 94 b onthe other side insulates the rest of the element sheets.

FIG. 29 shows front view of a 3 series 2 parallel stack 92 that iscomposed of element sheets with identical nanolinear pattern designs orprinted thin line and short thins line patterns and different terminalconfigurations. The element sheets 42 a, 42 c, and 42 e have been madewith terminals on both extremities on the top but only one extremity onthe bottom and are stacked at alternating orientations. The elementsheets 42 b, 42 d, and 42 f have been made with terminals on bothextremities on the top and on the bottom. The electrolyte applied to anelement sheet is contained by the element sheet where the electrolytehas been applied and the next element sheet. The cover element 95 withterminals on the same side and on only one extremity on the top and onthe bottom, and with no electrodes and no electrolyte is placed on thetop of the stack to contain the electrolyte of the previous elementsheet closing the 3 series 2 parallel stack 92.

The series gaps 94 a and 94 b divide the 3 series 2 parallel stack 92 inthree blocks, each made with two element sheets. The first block is madeby element sheets 42 a and 42 b connected by the terminal connections 93a and 93 b. The second block is made by element sheets 42 c and 42 dconnected by the terminal connections 93 d and 93 e. The third block ismade by element sheets 42 e and 42 f connected by the terminalconnections 93 g and 93 h. The first and the second blocks are connectedin series by the terminal connection 93 c and the second and thirdblocks are connected in series by the terminal connection 93 f. Theterminal connections 93 i makes the connection to the cover element 95and the series gap 94 c on the other side insulates the rest of theelement sheets.

To implement a stack able to provide certain voltage and current, asuitable combination of element sheets can be used to produce any typeof n by m stack where n blocks each made of m element sheets connectedin parallel are connected in series.

FIG. 30 shows an exploded view of one embodiment of a supercapacitorcomposed of a case 98 that has two device terminals 99 a and 99 b and astack of element sheets. In the case of FIG. 30 the supercapacitor isassembled with one parallel stack 89. An electrolyte seal 96 is madearound the area covered by the electrolyte to prevent leaks and twoterminal seals 97 a and 97 b are made to provide mechanical support,isolate the terminals 60 a and 60 b and improve contact among theseveral terminals in the individual element sheets. The electrolyte seal96 and the terminal seals 97 a and 97 b can be made using a glue stripor by applying heat to the necessary spots in the element sheets tocause them to melt and fuse together. As the terminals 60 a and 60 b inboth extremities of the parallel stack 89 are all connected, the deviceterminals 99 a and 99 b are constructed to go around the case 98 so theycan make contact to the terminals at both sides of the case.

FIG. 31 shows the assembled supercapacitor of FIG. 30, composed of thecase 98, two device terminals 99 a and 99 b and the parallel stack 89.

Detail FIG. 31A shows a device connection 100 a between the topmostterminal 60 a of the parallel stack and the device terminal 99 a. Thedevice connection 100 a can in most applications be made just bycontact, not requiring welding or complicated wiring, reducingmanufacturing complexity and costs.

FIG. 32 shows another embodiment of an assembled supercapacitor, in thiscase based on one series stack 90. As the series stack 90 has terminalson both sides of only one extremity of the case 98, the device terminals99 a and 99 b are made with a different design. The device terminals 99a and 99 b are embedded in the case 98 one at each side of the case atthe appropriate position to contact the terminals of the stack.

FIG. 32A shows the device connection 100 a between the device terminal99 a and the terminal 60 a of the series stack.

FIG. 33 shows another embodiment of an assembled supercapacitor, in thiscase based on one 2 series 3 parallel stack 91. A second alternativedesign for the device terminals 99 a and 99 b for stacks that haveterminals on both sides of only one extremity of the case 98 such as the2 series 3 parallel stack 91 is shown. The device terminals 99 a and 99b are made shorter to be placed at the same extremity of the case 98with some clearance between them.

Detail FIG. 33A shows the device connection 100 a between the deviceterminal 99 a and the terminal 60 a of the 2 series 3 parallel stack.

Detail FIG. 33B shows that a device terminal bypass 101 b allows thedevice terminal 99 b to pass above the terminal 60 a without touchingit. The device terminal 99 b and the terminal 60 a are separated by theuse wall.

FIG. 34 shows another embodiment of an assembled supercapacitor forstacks that have terminals on opposite extremities of the case 98 suchas the parallel stack. The device terminals 99 a and 99 b are placed atopposite extremities at the appropriate places to connect the terminalsof the stack.

Operation

FIG. 3 shows that as the perforation drum 44 rotates in the direction ofthe curved arrow, the element sheet 42 advances in synchronicity in thedirection of the straight arrow, the perforation spikes 45 a and 45 bproduce the orifices 43 a and 43 b in the intended positions in theelement sheet.

FIG. 6 shows that as the cylindrical pattern mask 50 rotates in thedirection of the curved arrow and the element sheet 42 advances insynchronicity in the direction of the straight arrow, the linear lightsource 52 produces a focused and collimated light of adequate wavelengththat illuminates the cylindrical pattern mask 50 producing a dynamicimage into the surface of the element sheet 42 sensitizing thephotoresist. The mask gap 51 generates a gap between two consecutiveelement sheets so they can later on be cut apart. The process isrepeated for both sides of the element sheet.

FIG. 25 shows the manufacturing method that can produce large quantitiesof element sheets stacked on top of each other at an affordable cost.The sheet heel 82 of thin plastic film, containing up to severalkilometers of continuous sheet 83 a is unrolled to feed the machinery.The continuous sheet 83 a is first perforated using the perforation drum44 or other suitable method to produce orifices in the requiredlocations. The continuous sheet 83 a then passes through a series ofwork stations 84 a, 84 b, 84 c, etc. where the other steps of theprocess are carried out.

In the printing process, work station 84 a prints the terminals, workstation 84 b prints the selected pattern of thin lines and short thinlines, work station 84 c dispense the electrolyte and the glue strip.

In the photoresist process, work station 84 a dispenses the photoresist,work station 84 b sensitizes the photoresist using a cylindrical patternmask as described in FIG. 6 or another suitable method. The work station84 c removes the areas of the photoresist and subsequent work stations(not drawn to avoid cluttering) dispense the ink, remove eventual inkspills, remove the remaining photoresist, dispense the electrolyte andthe glue strip.

Several continuous sheets 83 b, 83 c, 83 d, 83 e, etc. under tension toallow the proper alignment of the terminals using guide rollers 85 a, 85b, etc. are then pressed together and glued producing the stacked sheet86. The stacked sheet 86 is cut first in the direction of the movementproducing parallel width cut sheets 87 that are subsequently cut in theperpendicular direction of the movement producing length cut sheets 88in the designed size. Depending on the sequence of the element sheetsprinted into the different continuous sheets, a variety of stacks can beproduced.

FIG. 35 shows a cross-sectional view of a portion of the element sheet42 already perforated by orifices 43 that serves as a substrate for thephotoresist 46. The photoresist 46 may be applied to the element sheet42 through spin coating, spraying, roller coating, dip coating,extrusion coating or other similar process to spread the photoresist 46evenly over the surface of the element sheet 42. The coating process mayalso optimize the thickness T_(C) of the photoresist 46 to provideadequately dimensioned structural surfaces that form the physicalbarriers to contain the special grapheme and/or carbon based inks. Forexample, using a roller coating process that is suitable to integrate ina process described in FIG. 25 the photoresist 46 may be spread using aroller that is kept at a constant distance from the element sheet 42setting the thickness T_(C) of the photoresist 46. The thickness T_(C)of the photoresist 46 may in some embodiments be in a range of 1 μm-10μm or in other ranges depending on the energy density and power densitydesired.

FIG. 36 shows a cross-section of a portion of a pattern mask 47 alignedover the photoresist 46 to expose partial areas of the photoresist 46 tothe light source 49. A developer solution is applied to wash the exposedportions away from the photoresist 46 and leave a set of cavities 55surrounded by physical barriers 56 and exposing the orifices 43.

FIG. 37 illustrates the deposition of ink 58 from the printer head 57that due to settling and splatter is generally greater than 5 μmdepending upon the ink's composition and viscosity. Using the process ofthe present invention, the special ink 58 made of graphene, grapheneoxide, activated carbon, carbon nanotubes or other mixtures are printedwithin the cavities formed by the physical barriers 56 of photoresist.As shown multiple cavities 55 may be formed within a very small area andwithin areas much smaller than the 5 μm minimally necessary for thedeposition of ink 58 on an element sheet 42 having only a flat surface.

As shown in FIG. 38, the thickness T_(C) of the photoresist layer 46provides for ink 58 a to fill or partially fill the cavities providingfor increased amounts of ink 58 a within very small areas increasing thesurface area of the graphene and carbon components and therebyincreasing energy storage. This allows the ink 58 a to reach all spotsintended to be covered without the risk of leaks or spills that couldlead to short circuits. The deposited ink 58 b flows through and fillsthe orifices 43 reaching the other side of the element sheet 42.

At this point in the process, the ink 58 a, 58 ba can be submitted to acuring process or be left to dry on its own before the physical barrieris removed. In some embodiments, the graphene and/or carbon based inkmay be made with tiny particles using a binder of low viscosity or maybe made with a binder that will not harden unless submitted to asuitable curing process to solidify the ink to form the pattern designsas described herein. In the event that the ink overflows the volume ofthe cavities 55 a process can be used to remove the excess ink withoutdamaging the ink deposited inside the cavities as described in FIG. 12.

FIG. 39 illustrates that after the ink 58 a, 58 b has dried, a processstep to expose the remaining areas of photoresist to the light source 49is carried out so that all photoresist can be washed away from theelement sheet 42.

FIG. 40 illustrates a process step of printing the electrolyte 63 withinthe pattern designs formed from the graphene, and/or carbon based ink 58a, 58 b. The electrolyte 63 flows into the gaps left by the removedphotoresist and can be sealed using a glue strip or by applying heat.

The individual element sheets of the supercapacitor are made and stackedaccording to the specified voltage and current ratings desired. Toincrease the current and the energy stored a block of element sheetsstacked in parallel is used and to increase the voltage, identicalblocks of one or more element sheets are stacked in series. Theterminals are constructed to have a much larger size than the individualfringe to enable the individual element sheets to be easily stackedwithout the need to precisely align them, facilitating the constructionof the devices and reducing costs. The larger size of the terminals alsofacilitates the conductance of large currents improving the maximuminstantaneous power that a device is able to supply.

The operation of the supercapacitor is very simple and follows thestandard practice of such devices. The supercapacitor can be charged anddischarged using an appropriate circuit that ensures that the maximumcurrent is not exceeded during charge or discharge.

CONCLUSION

A set of pattern designs to construct element sheets is proposed thatfacilitates the construction of supercapacitors using thin sheets thatcan be printed using graphene based inks. The proposed patterns are mademostly of parallel straight lines allowing the patterns to be alignedwith the direction of the printing. This facilitates the deposition ofthe ink and reduces printing errors and costs.

The proposed patterns also contain terminals of a larger size comparedto the other printed features on the element sheet that connect bothsides of the element sheet through a series of connecting orifices. Theterminals simplify the assembly of a stack of element sheets, necessaryto achieve the desired voltage, current and charge ratings, enabling theindividual printed sheets to be placed on top of each other without theneed of individual welds, metallization or complicated process ofalignment. The connections are made easily and reliably just by theplacement of the individual sheets on the stack.

The electrolyte in the sheets can be sealed inside the stack with a gluestrip or using a heat sealing process and the sealed stack can be simplyplaced inside a case without the need of welding unless a more demandingapplication requires a more stable connection.

The photoresist process allows the printing of very small structuresusing photoresist enabling the construction of devices with higherenergy density without increasing the weight of the device.

The standard printing process allows the construction of cheaper devicesthan the ones produced with the photoresist process by using standardprinting equipment albeit producing devices with smaller energy density.

The combination of more efficient designs, simpler assembly process andsmaller structures produce better supercapacitor devices at affordableprices.

The invention has been described in detail with particular reference tocertain preferred embodiments thereof, but it will be understood thatvariations and modifications can be effected within the spirit and scopeof the invention.

What is claimed is:
 1. A manufacturing process for the production ofsupercapacitors having increased energy density, comprising: perforatinga series of orifices on an element sheet; layering the element sheetwith photoresist on one or both sides; exposing portions of thephotoresist to a light source to remove these portions from the elementsheet; printing graphene ink within the remaining portions of thephotoresist and through the orifices; printing graphene ink on bothsides of the element sheet filling the orifices to create terminals thathave a larger size as compared to the remaining portions and to connectboth sides of the element sheet; removing remaining portions ofphotoresist thereby leaving a pattern design; printing electrolytewithin the pattern design; and wherein the pattern design formingelectrodes having minimal spacing between gaps to increase the energydensity within the supercapacitor.
 2. The manufacturing process for theproduction of supercapacitors of claim 1 wherein the minimal gapsbetween the printed electrodes is less than five microns.
 3. Themanufacturing process for the production of supercapacitors of claim 1wherein the minimal gaps between the printed electrodes is between onehundred nanometers to two microns.
 4. The manufacturing process for theproduction of supercapacitors of claim 1 comprising increasing thethickness of the photoresist to increase the depth of the graphene inklayer and the electrolyte layer thereby increasing the energy density ofthe supercapacitor.
 5. The manufacturing process for the production ofsupercapacitors of claim 1 comprising replacing the graphene ink by anink composed of a mixture selected from the group consisting ofgraphene, carbon nanotubes and activated carbon to increase the physicalproperties of the electrodes by increasing the number of pores into theelectrodes thereby increasing the available surface area of the printedelectrode and thereby increasing the capacitance and the energy densityof the supercapacitor.
 6. The manufacturing process for the productionof supercapacitors of claim 1 comprising a pattern design havingphysical barriers that extend linearly in the direction of printing. 7.The manufacturing process for the production of supercapacitors of claim1 comprising a pattern design that maximizes the number of individualcapacitors that can be printed within the element sheet.
 8. Themanufacturing process for the production of supercapacitors of claim 1comprising individual capacitors connected in parallel.
 9. Themanufacturing process for the production of supercapacitors of claim 1comprising individual capacitors connected in series.
 10. Themanufacturing process for the production of supercapacitors of claim 1comprising individual capacitors connected in series and parallel. 11.The manufacturing process for the production of supercapacitors of claim1 comprising a pattern design comprising individual fringes of theelectrode terminating in a curved end with a matching curved contour onan adjacent electrode.
 12. The manufacturing process for the productionof supercapacitors of claim 1 comprising stacking element sheets inparallel to increase the capacitance and the current of thesupercapacitor.
 13. The manufacturing process for the production ofsupercapacitors of claim 1 comprising stacking element sheets in seriesto increase the voltage of the supercapacitor.
 14. The manufacturingprocess for the production of supercapacitors of claim 1 comprisingstacking element sheets in series and parallel to increase the voltage,capacitance and current of the supercapacitor.